Method for measuring amounts of components and calorific value of coal gas

This application is a continuation-in-part of International Patent Application No. PCT/CN2012/080795 with an international filing date of Aug. 30, 2012, designating the United States, now pending, and further claims priority benefits to Chinese Patent Application No. 201110435862.3 filed Dec. 22, 2011. The contents of all of the aforementioned applications, including any intervening amendments thereto, are incorporated herein by reference.

The invention relates to a method for measuring the components and calorific value of coal gas.

As a typical manual chemical analyzer, Orsat gas analyzer is characterized by low price, convenient operation and easy maintenance. However, the manual operation has low accuracy and low speed, and cannot meet the needs of industrial development. In recent years, the chromatograph has been promoted widely, but the gas to be tested must be separated using a plurality of chromatographic columns in the presence of a carrier gas, which causes the difficulty in the real-time online test.

Infrared gas analyzers have been used for years, but the technology can only analyze one or two components. In addition, gas analyzers suffer from high price and complex maintenance, and cannot accurately measure the amount of CH 4 in the coal gas due to interference from other hydrocarbons. The volume concentration of H 2 and O 2 in the coal gas cannot be measured using a nondispersive infrared (NDIR) method. The volume concentration of H 2 is usually measured with a thermal conductivity detector (TCD), and that of O 2 is measured with an electrochemical detector (ECD). CH 4 and other C n H m in the coal gas interfere with each other, and CH 4 and CO 2 interfere with H 2 .

Due to the significant mutual interference of C n H m and CH 4 , it is very difficult to accurately measure various components in the coal gas, especially CH 4 , C n H m , CO and H 2 which provide the main source of calorific value. Therefore, it is necessary to develop a method to accurately measure a variety of components in the coal gas, calculate the calorific value of coal gas, and effectively eliminate the interference between gases.

In view of the above-described problems, it is one objective of the invention to provide a method for more accurately measuring the components and calorific value of coal gas.

To achieve the above objective, in accordance with one embodiment of the invention, there is provided a method for measuring the components and calorific value of coal gas, the method comprising the following steps:

1) measuring a volume concentration of H 2 (T H2 ) using a thermal conductivity detector (TCD), measuring a volume concentration of O 2 using an electrochemical detector (ECD); 2) measuring volume concentrations of CO, CO 2 , CH 4 , and C n H m in the coal gas, represented by T CO , T CO2 , T CH4 , and T CnHm , respectively, using a non-dispersive infrared (NDIR) technology; 3) revising an interference of CH 4 in C n H m using an equation R CnHm =T CnHm −A×T CH4 , in which, A represents an undetermined coefficient, and T CnHm and T CH4 represent the volume concentrations of C n H m and CH 4 measured with the NDIR, respectively; 4) revising a measured volume concentration of H 2 using the equation R H2 =T H2 −a×(T CH4 +R CnHm )−b×T CO2 , in which, T H2 represents the measured volume concentration of H 2 using the TCD, T CH4 and T CO2 represent the volume concentrations of CH 4 and CO 2 measured using the NDIR, respectively, R CnHm represents a revised volume concentration of C n H m , and a and b represents undetermined coefficients; and 5) calculating the calorific value of the coal gas using the equation Q=T CO ×12.64+R H2 ×18.79+T CH4 ×35.88+R CnHm ×93.18, in which, T CO and T CH4 represent measured volume concentrations, and R H2 and R CnHm represent revised volume concentrations.

In a class of this embodiment, in the process of measuring the volume concentration of CH 4 using the NDIR, a center wavelength (CWL)/half-peak bandwidth (HWBP) of a selected narrowband filter is 7.85±0.05 μm/180±5 nm.

In a class of this embodiment, in the process of measuring the volume concentration of C n H m using the NDIR, a CWL/HWBP of a selected narrowband filter is 3.46±0.05 μm/120±5 nm.

In a class of this embodiment, in the process of measuring the volume concentration of CO using the NDIR, a CWL/HWBP of a selected narrowband filter is 4.66±0.05 μm/90±5 nm.

In a class of this embodiment, in the process of measuring the volume concentration of CO 2 using the NDIR, a CWL/HWBP of a selected narrowband filter is 4.26±0.05 μm/120±5 nm.

Compared with the existing test methods, the method according to embodiments of the invention has the following advantages: the invention can simultaneously measure a variety of gas components, reduce the interference between different gases by optimizing NDIR narrowband filter parameters, measure C n H m with the filter of 3.46 μm wavelength, convert other hydrocarbons into C 3 H 8 , and facilitate calculating the calorific value of coal gas according to the obtained volume concentration of gas. The manufacturing cost of the analytical instrument in this method is ⅓ as much as that of the calorimeter in the traditional combustion method, and only 1/10 as much as that of the mass spectrum analyzer. Its analysis speed is 30 times more than that of the conventional chromatograph.

FIG. 1 is a principle diagram for analysis of components and calorific value of coal gas in accordance with one embodiment of the invention;

FIG. 2 is an infrared absorption spectrum of CO, CO 2 and CH 4 ;

FIG. 3 is a mutual interference pattern of hydrocarbons approximately at 3.3 μm; and

FIG. 4 is an infrared absorption spectrum of CH 4 .

For further illustrating the invention, experiments detailing a method for measuring the components and calorific value of coal gas are described hereinbelow combined with examples.

1. Selection of Various Gas Filter Parameters, Gas Chamber Length, and Measuring Range of Gas Detectors.

As shown in the infrared absorption spectra of CO and CO 2 in FIG. 2 , the absorption peak of CO at 4.66 μm is not affected by CO 2 , and the absorption peak of CO 2 at 4.26 μm is not affected by CO. Thus, a CO detector with the measuring range of 40% and a CO 2 detector with the measuring range of 30% are made, with the narrowband filter parameters respectively of 4.66 μm/90 nm and 4.26 μm/120 nm, reference channel of 3.91 μm, and chamber length respectively of 43 mm and 2 mm.

Then, based on the infrared absorption spectra of CH 4 , C 2 H 6 , C 3 H 8 and C 4 H 10 in FIGS. 3-4 , the absorption peak at 7.85 μm is selected, instead of the absorption peak at 3.3 μm, in order to eliminate the influence of C n H m on CH 4 absorption peak. As a result, the CH 4 detector with the measuring range of 20% is made, with the narrowband filter parameters of 7.85 μm/180 nm, reference channel of 3.91 μm and CH 4 chamber length of 68 mm.

According to the infrared absorption spectrum of C n H m in FIG. 3 , C n H m has absorption peaks at 3.3-3.5 μm. In order to reduce the influence of CH 4 on C n H m , it is necessary to avoid the absorption peak of CH 4 , and select center wavelength at 3.35-3.5 μm. Test of different filters at 3.35-3.5 μm shows that C 3 H 8 can represent C n H m (C n H m is calibrated with C 3 H 8 ) with the narrowband filter of 3.46 μm/120 nm as the filter for C n H m detector. The C n H m detector with the measuring range of 5% is made, with the reference channel of 3.91 μm and C n H m chamber length of 43 mm. The test data are provided in Table 1.

From the comparison of Table 1 and Table 2, the proportionality coefficient of the volume concentration of C n H m measured with the detector made of the narrowband filter at 3.46 μm/120 nm is very close to its coefficient of calorific value, so the calorific value of C n H m can be calculated as that of C 3 H 8 .

Likewise, a TCD of H 2 with the measuring range of 20% and an ECD of O 2 with the measuring range of 25% are manufactured according to conventional methods.

2. Measurement of the Volume Concentration of Various Gases

CO, CO 2 , CH 4 and C n H m are measured using NDIR, and the readings are respectively expressed as T CO , T CO2 , T CH4 and T CnHm .

The volume concentration of H 2 is measured with a TCD, and is expressed as T H2 .

The volume concentration of O 2 is measured with an ECD, and is expressed as T O2 .

3. Revision of the Gas Volume Concentration and Calculation of the Calorific Value.

1) Revise the Volume Concentration of C n H m with CH 4 .

CH 4 has certain influence on C n H m , so it is also necessary to get the revised volume concentration of C n H m (R CnHm ) through revising the measuring result of C n H m (T CnHm ) obtained from the calibration curve according to the volume concentration of CH 4 (T CH4 ).

In order to revise the influence of CH 4 on the measuring result of C n H m , the calibrating gas CH 4 is introduced into the six-component gas analyzer present in the biomass gasification system of this example. Volume concentration and measuring result of the calibrating gas are provided in Table 3.

The following correction equation can be obtained through data analysis:

R CnHm =T CnHm −A×T CH4

Data in Table 3 are substituted into the equation to conclude that A=0.02868.

Therefore,

R CnHm =T CnHm −A×T CH4 =T CnHm −0.02868 ×T CH4

2) Revise the Volume Concentration of H 2 .

The balance gas N 2 used to calibrate H 2 is greatly different from CH 4 and CO 2 in the relative thermal conductivity, as shown in Table 4, so CH 4 and CO 2 have certain influence on the measuring results of H 2 using an TCD. C n H m is different from N 2 in the thermal conductivity, but its content in the coal gas is only about ⅕ as much as CH 4 , therefore it can be neglected. CO and O 2 are very slightly different from N 2 in thermal conductivity, and can also be neglected. Hence, it is only necessary to get the revised volume concentration of H 2 (R H2 ) through revising the measuring results of H 2 (T H2 ) according to the measuring results of CH 4 and CO 2 (T CO2 , T CH4 ).

In order to revise the influence of CH 4 and CO 2 on the measuring result of H 2 , the calibrating gases CH 4 and CO 2 are introduced into the six-component gas analyzer present in the biomass gasification system of this example. Volume concentration and measuring result of the calibrating gases are provided in Table 5:

The following correction equation can be obtained through data analysis:

R H2 =T H2 −a×T CH4 −b×T CO2

Data in Table 5 are substituted into the equation to conclude that a=0.13989; b=−0.11026.

Therefore,

R H2 =T H2 −a×T CH4 −b×T CO2 =T H2 −0.13989 ×T CH4 +0.11026× T CO2 .

3) Calculate the Calorific Value of Coal Gas

According to the above gas concentration, the calorific value of coal gas is obtained through substituting T CO , T CH4 , R CnHm and R H2 into the equation Q=T CO ×12.64+R H2 ×18.79+T CH4 ×35.88+R CnHm ×93.18; in which, Q is expressed as MJ/m 3 , 12.64, 18.79, 35.88 and 93.18 are respectively the coefficient of low calorific value of CO, H 2 , CH 4 and C n H m expressed as MJ/m 3 .

This example is provided to design a six-component gas analyzer with the measuring range of CO of 40%, that of CO 2 of 30%, that of CH 4 of 20%, that of C n H m of 5%, that of H 2 of 20%, and that of O 2 of 25%. This gas analyzer is applicable to many industries, such as air coal gasification, biomass air gasification, blast furnace, and endothermal and exothermal gas generators for heat treatment.

Example 2 Gas Analysis of Coal Gas from Biomass Pyrolysis and Coking Using Six-Component Gas Analyzer

1. Selection of the Length and Measuring Range of Various Gas Chambers

Filters in the NDIR gas detector are selected as that in Example 1. Gas chamber design: CO detector with the measuring range of 40% and CO chamber length of 43 mm; CO 2 detector with the measuring range of 20% and CO 2 chamber length of 3 mm; CH 4 detector with the measuring range of 50% and CH 4 chamber length of 34 mm; C n H m detector with the measuring range of 10% and C n H m chamber length of 20 mm.

A H 2 detector with the measuring range of 75% and O 2 detector with the measuring range of 25% are manufactured according to conventional methods.

2. Measurement of the Volume Concentration of Various Gases

CO, CO 2 , CH 4 and C n H m are measured using NDIR, and the readings are respectively expressed as T CO , T CO2 , T CH4 and T CnHm .

The volume concentration of H 2 is measured with a TCD, and is expressed as T H2 .

The volume concentration of O 2 is measured with an ECD, and is expressed as T O2 .

3. Revision of the Gas Volume Concentration and Calculate the Calorific Value.

1) Revise the Volume Concentration of C n H m with CH 4 .

In order to revise the influence of CH 4 on the measuring result of C n H m , the calibrating gas CH 4 is introduced into a six-component gas analyzer present in the biomass pyrolysis and coking system of this example. Volume concentration and measuring result of the calibrating gas are provided in Table 6:

The following correction equation can be obtained through data analysis:

R CnHm =T CnHm −A×T CH4

Data in Table 6 are substituted into the equation to conclude that A=0.02837.

Therefore,

R CnHm =T CnHm −A×T CH4 =T CnHm −0.02837 ×T CH4

2) Revise the Volume Concentration of H 2 .

In order to revise the influence of CH 4 and CO 2 on the measuring result of H 2 , the calibrating gases CH 4 and CO 2 are introduced into the six-component gas analyzer present in the biomass pyrolysis and coking system of this example. Volume concentration and measuring result of the calibrating gases are provided in Table 7:

The following correction equation can be obtained through data analysis:

R H2 =T H2 −a×T CH4 −b×T CO2

Data in Table 7 are substituted into the equation to conclude that a=0.14097; b=−0.11091.

Therefore,

R H2 =T H2 −a×T CH4 −b×T CO2 =T H2 −0.14097 ×T CH4 +0.11091 ×T CO2

3) Calculate the Calorific Value of Coal Gas

According to the above gas concentration, the calorific value of coal gas is obtained through substituting T CO , T CH4 , R CnHm and R H2 into the equation Q=T CO ×12.64+R H2 ×18.79+T CH4 ×35.88+R CnHm ×93.18, in which, Q is expressed as MJ/m 3 , 12.64, 18.79, 35.88 and 93.18 are respectively the coefficient of low calorific value of CO, H 2 , CH 4 and C n H m expressed as MJ/m 3 .

This example is provided to design a six-component gas analyzer with the measuring range of CO of 40%, that of CO 2 of 20%, that of CH 4 of 50%, that of C n H m of 10%, that of H 2 of 75%, and that of O 2 of 25%. This gas analyzer is applicable to many industries, such as coking, biomass pyrolysis, dry distillation, and mixed gas in steel.

While particular embodiments of the invention have been shown and described, it will be obvious to those skilled in the art that changes and modifications may be made without departing from the invention in its broader aspects, and therefore, the aim in the appended claims is to cover all such changes and modifications as fall within the true spirit and scope of the invention.